Ammonium Acetate → Ethyl 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta[B]pyrrole-3-carboxylate

HRID 1290087

反応式

HRID 1290087 の反応式
[O:1]=[C:2]1[C:11]2[C:10]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9]O[C:7]=2[CH2:6][CH2:5][CH2:4][CH2:3]1.C([O-])(=O)C.[NH4+:21]>CN(C)C=O>[O:1]=[C:2]1[C:11]2[C:10]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9][NH:21][C:7]=2[CH2:6][CH2:5][CH2:4][CH2:3]1

参加物

4

反応物 2

HCID 517165Ammonium AcetateHCID 18696560ethyl 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan-3-carboxylate

生成物 1

HCID 18696565Ethyl 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta[B]pyrrole-3-carboxylate収率 50.7%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
115 °C

実験手順

A mixture of ethyl 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]furan-3-carboxylate (3.48 g,15.7 mmol) and ammonium acetate (2.41 g, 31.3 mmol) in N,N-dimethylformamide (25 mL) was heated at 115° C. for 6 hours. The mixture was concentrated in vacuo, ice water was added, and extracted 2X with dichloromethane. The combined organic layers were washed with saturated aqueous sodium bicarbonate then brine, dried over sodium sulfate, filtered through a small pad of Silica gel (5% methyl alcohol/dichloromethane), and the filtrate concentrated in vacuo to give ethyl 4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylate (1.76 g). A solution of this ester in aqueous 5N sodium hydroxide (30 mL) and ethyl alcohol(6 mL) was heated at reflux for 1 hour, then cooled in an ice bath. The mixture was acidified with hydrochloric acid; the resulting precipitate was collected, rinsed with water followed by diethyl ether and allowed to dry to give 4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylic acid (1.17 g). m.p. 225°-227°C.

後処理

  1. concentrationThe mixture was concentrated in vacuo, ice water
  2. additionwas added
  3. extractionextracted 2X with dichloromethane
  4. washThe combined organic layers were washed with saturated aqueous sodium bicarbonate
  5. dry with materialbrine, dried over sodium sulfate
  6. filtrationfiltered through a small pad of Silica gel (5% methyl alcohol/dichloromethane)
  7. concentrationthe filtrate concentrated in vacuo

出典と根拠

ORDレコード
ord-eb7882379a2d48b3ba19c20e616e58b7
出典データセット
uspto-grants-1998_05
特許番号
US05750702

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